McClare C W
Ciba Found Symp. 1975(31):301-25. doi: 10.1002/9780470720134.ch16.
Two misleading conclusions drawn from the classical treatment of thermodynamics are, first, that single molecules cannot be treated thermodynamically and, second, that all real processes must be irreversible. The first conclusion has meant that the disruptive effect of thermal motions has been ignored, the second has meant that dynamic forces which cannot exist without stored energy, have been left out of account. The effect of these beliefs is demonstrated by analysis in detail of a simple electrostatic model of muscle. It is shown that the necessity of protecting each step against decay of the stored energy, and the requirement that each should be specific, has the effect of stopping the model actually working. Moreover, the character of static forces, which are strongest after their stored energy has been used up, precludes their use in cyclic processes because as much stored energy is required to undo them later in the cycle. Covalent intermediates are also examined from a quantum mechanical viewpoint and it is shown how these store energy which can be transferred by resonant transitions in the ground state when groups like phosphate are transferred chemically between molecules. But this analysis shows that, necessarily, the energy remains stored and therefore not available for muscular contraction. Then it follows naturally both that bond vibrations are produced in exothermic chemical reactions and that, because the force disappears when the energy has been used up, resonant exchange of stored energy in the excited state should solve the difficulties of previous approaches to these problems.
第一,单个分子不能用热力学方法处理;第二,所有实际过程必然是不可逆的。第一个结论意味着忽略了热运动的破坏作用,第二个结论意味着没有考虑到没有储能就不可能存在的动力。通过对肌肉的一个简单静电模型进行详细分析,证明了这些观点的影响。结果表明,保护每一步骤防止储能衰减的必要性以及每一步骤都应具有特异性的要求,导致该模型实际上无法运行。此外,静力的特性是在其储能被耗尽后最强,这使得它们不能用于循环过程,因为在循环后期需要同样多的储能来消除它们。还从量子力学的角度研究了共价中间体,展示了它们如何储存能量,当磷酸基团等基团在分子间进行化学转移时,这些能量可以通过基态的共振跃迁进行转移。但该分析表明,能量必然会保持储存状态,因此无法用于肌肉收缩。于是自然而然地得出,在放热化学反应中会产生键振动,并且由于能量耗尽时力就会消失,所以激发态下储能的共振交换应该能解决以往处理这些问题的方法中存在的困难。